Interpolymerization products of diene synthesis products and compounds having an omega-methylene group and process of their production



Patented Sept. 26,

. Q' Q I. v I 2,359,038 UNITED \STATEIS PATENT OFFICEINTERPOLYMERIZATION PRODUCTS O DIENE SYNTHESISPBODUCTS AND COM- POUNDSHAVING GROUP AND PROCESS OF THEIR PRO u-DIETHYLENE Heinrich Hopi! andWilhelm Rapp, Ludwigshafen-on-the-Bhine,

, assignors,- by. AnilineaFilm Corporation, New York, N. Y., acorporation of Delaware No Drawing. Application June 16, 1939, SerialN0. 279,488. In Germany July 12, 1938 u 10 Claims. (01.260-7'8) Thepresent invention relates t8 polymerization products and a process ofproducing same.

It is already known that dienes may be added on to substances having adouble or triple carbon linkage activated by substituents with theformation of cyclic unsaturated compounds. This reaction is generallyknown as the diene synthesis." For example from butadiene and maleicanhydride there is formed tetrahydrophthalic anhydride corresponding tothe following scheme:

CH, CH:

' CHI-CO C CH-CO CH v 8 -v 0 H H-CO UH UH CO CH: a

The addition products thus obtained cannot be polymerized by the usualpolymerization methods We have now found that the diene synthesisproducts (the said addition products of dienes and compounds havingdouble or triple carbon linkages activated by substituents) can bepolymerized together with organic compounds containing an w-methylenegroup. Addition comof butadiene and its substitution products, such asisoprene, dimethyl-butadiene and beta-chlorbutadiene, and alsocyclopentadiene and -hexadiene, with an unsaturated organic compoundcontaining the atomic grouping such as maleic anhydride, maleic acidesters, maleic acid imides, vinyl compounds having a carbonyl groupadjacent to the vinyl group, such as acrolein, vinyl methyl ketone, andalso crotonaldehyde, cinnamic aldehyde, -cinnamic acid ester, acrylicacid or methacrylic acid and their derivatives, and vinyl esters, andother comticular their esters, vinyl esters, vinyl chloride, vinylethers, N-vinylcarbazole, butadiene and chlorbutadiene.

The interpolymerization products of the said addition compounds with thepolymerizable compounds may take place by anyof the known 5 as forexample alkylated naphthalene sulphonic pounds of the said kind are forexample those methods of polymerization, as for example by heating, ifdesired in the presence of polymerization' accelerators, such as benzoylperoxide, acetyl peroxide, hydrogen peroxide or by treating withacid-reacting inorganic halides, as for example boron fluoride.Frequently'it is preferable to carry out the polymerization in aqueousemulsion with an addition of dispersing agents,

acids, sulphuric acid esters of higher fatty alcohols, addition productsof several molecules of ides. of higher fatty acids or sulphonated fattyacid amides. In many cases it is preferable to stabilize thepolymerization products by after-' treatment with basic substances, suchas caustic alkali or soda solutions.

The interpolymerization products obtained are from soft rubber likemasses to hard masses depending on the initial materials used. Theharder polymerization products may be drawn out into foils by themethods usual in the Celluloid industry or may be converted on extrusionpresses into tubes, rods or other shaped articles. The softinterpolymerization productsmay be worked similarly to rubber.

The following examples will further illustrate how this invention may becarried out in practice, but the invention is not restricted to theseexamples. The parts are by weight.

Example 1 dilute sponding to pH=3.5. The dispersion ofinterpolymerization product thus obtained is freed from monomericconstituents by treatment with Example 2 An emulsion of 200 parts ofacrylic acid methyl ester and 50 parts of tetrahydrophthalic aciddimethyl ester in 750 parts of water containing from to 12 parts ofalpha-hydroxyoctodecane sulphonic acid sodium salt dissolved therein ispolymerized as described in Example 1 and the polymerization productdispersion worked up in a corresponding manner. A good yield oi a pale,tough, rubber-like polymerization product is obtained. 1

A pale rubber-like mass is obtained in the same way from 200 parts ofacrylic acid methyl ester and 50 parts or methyl cyclohexene carboxyiicacid ethyl ester.

Example 3 An emulsion of 100 parts of vinyl chloride and 25 parts oftetrahydrophthalic acid diethyl ester in 400 parts oi. water containing6 parts of alphahydroxyoctodecane sulphonic acid sodium salt dissolvedtherein is polymerized, after the addition of from 0.6 to 1 part ofpotassium persulphate and hydrogen peroxide, at a pH of 3.5 in apressure-tight vessel for 24 hours at 50 C. while mixing well. Thedispersion oi polymerization product thus obtained has aluminum sulphateadded thereto. The polymerization product thus precipitated is treatedat from 60 to 80 C. with about 0.5 per cent of sodium hydroxidesolution, centrifuged, washed until neutral with water, then washedwith'methanol and dried. The dried material contains 50.4 per cent ofchlorine, corresponding to 88 er cent 01 vinyl chloride. The resultinginterpolymerization product is a pale granular powder which may bepressed hot into colorless shaped articles.

In the same way, from 250 parts of tetrahydrophthalic acid ethyl esterand 250 parts of vinyl chloride, an interpolymerization product isobtained having a chlorine content oi 40.1 per cent, corresponding to70.5 per cent of vinyl chloride.

Example 4 Emample 5 A mixture of 80 parts of styrene and 20 parts oftetrahydrophthalic acid dimethyl ester and 0.5 part of benzoyl peroxideis slowly heated to from 150, to 160 C. Within. 2 hours, it haspolymerized to a glass-clear solid mass.

A solid glass-clear interpolymerization prod-i5 uct is obtained in thesame way from parts of styrene and 20 parts of methylcyclohexene.

carboxylic acid ethyl ester.

' Example 6 Example 7 112 parts 01' p-chlorbutadiene and 38 parts oftetrahydrophthalic acid diethyl ester are emulsiiled in parts 01 a 4 percent aqueous solution of the condensation product 01 1 molecularproportion of p.p-dichlordiethyl ether and 2 molecular proportions of amixture oi amines prepared irom the nitriles oi fatty acids obtained byoxidizing paramn wax. The emulsion obtained is added with 2 parts of 30per cent hydrogen,

peroxide and 0.1 part of potassium persulphate and heated at 40 C. for24 hours while stirrine.

The dispersion oi the interpolymerization product thus formed is addedwith methanol, whereby the interpolymerization product is coagulated inthe form or flocks. These flocks are washed with water, dried androlled. A solid sheet is thus obtained. The interpolymerization productcan be vulcanized in the usual manner.

What we claim is:

, l. Interpolymerization products or vinyl chloride and atetrahydrophthalic acid ester.

2. Interpolymeri'zation products of styrene and a tetrahydrophthalicacid ester.

3. Interpolymerization products of chlorbutadiene and atetrahydrophthalic acid ester.

4. A process of producing interpolymerization products which comprisesheating a, compound having a group of the general formula wherein X isselected from the class consisting of hydrogen and alkyl and the CH2group stands in the w-position, said compound being selected from thegroup consisting of styrene, acrylic acid esters, methacrylic acidesters, vinyl chloride, N -vinyl carbazole, butadiene andchlorbutadiene, with a cyclic unsaturated addition product of a dieneselected from the class consisting of butadiene,'isoprene, dimethylbutadiene, p-chlorbutadiene, cyclopentadiene, and cyclohexadiene, and anunsaturated organic compound contain ing the atomic grouping andselected from the class consisting of maleic anhydride, maleic acidesters, acrolein, vinylmethyl ketone, crotonaldehyde, cinnamic aldehyde,acrylic acid, methacrylic acid, and methacrylic acid ethyl ester.

5. The process as defined in claim 2 wherein said components are heatedto a temperature oi 40 to C.

6. The process as defined in claim 2 wherein said components are heatedin the presence of a peroxide acting as a polymerization accelera- 7.The process as defined in claim 2 wherein the components are heated inthe presence 0! boron fluoride as a polymerization accelerator.

8. A process of producing interpolymerization products which comprisesheating a mixture 01 chlorbutadiene and a tetrahydrophthalic acid ester.A

9. The process of producing interpolymerization products which comprisesheating a mixture of vinyl chloride and a tetrahydrophthalic acid ester.

10. Interpolymerization products of a compound having the generalgrouping -CX=CH2 wherein X is selected from the group consisting ofhydrogen and allryl and the CH: group stands in the u-posltion, saidcompound being selected from the class consisting of styrene. acrylicacid esters. methacrylic acid esters, vinyl chloride, N-vinyl carbazole,butadiene and chlorbutadiene and a cyclic unsaturated addition compoundot a diene selected from the class con- -aisting of butadiene. isoprene.dimethylbutadiene,

p-chlorbutadiene, cyclopentadiene. and cyclohexadiene, with anunsaturated organic compound containing the atomic grouping o -c=candselected from the class consisting oi maleic anhydride. maleic acidesters. acrolein, vinylmethyl ketone, crotonaldehyde, cinnamic aldehyde,acrylic acid, methacrylic acid, and methacrylic acid esters.

, HEINRICH HOPFF.

WILHELM RAPP.

Certificate of Correction Patent N 0. 2,359,038. September 26, 1944.

HEINRIOHEHOPFF ET AL. I It is hereby certified that errors appear in theprinted specification of the above numbered patent re luring correctionas follows: Page 2, second column, lines 68,

71, and 75, for the c aim reference numeral 2 read 4; and that the saidLetters Patent should be read with these corrections therein that thesame may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of May, A. D 1947.

First Assistant Oommz'aaz'oner of Patents.

